JPH07199391A - Photograph element containing alkynyl amine doping agent - Google Patents

Abstract

PURPOSE: To provide a sensitive photographic element which shows high sensitivity but shows high sensitivity without showing substantial desensitization when mechanical pressure is applied to it by containing silver halide particles containing an alkinyl amine doping agent to form a silver halide emulsion. CONSTITUTION: When an alkinyl amine doping agent is present, a photographic element is given advantageous property of high sensitivity. Here, the photographic element is formed by containing silver halide particles containing a compound represented by the formula, Y-NHCH2 C-CR<3> . In the formula, R<3> is a hydrogen atom, aliphatic, carbocyclic or heterocyclic group and may be either the substituted or unsubstituted one and preferably R<3> is other than hydrogen, and more preferably is a 1-20C alkyl group and optimally is a methyl group, Y represents a nitrogen containing heterocyclic component, and in the presence of the doping agent having this, the silver halide particles of the silver halide emulsion is precipitated.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to photographic elements containing certain doping agents and having improved sensitivity.

[0002]

In conventional photographic techniques, a light-sensitive material, i.e. a silver halide grain, is exposed to actinic radiation,
It forms what is referred to in the art as a "latent image." A "latent image" is a useful visible image invisible precursor that emerges upon photographic development; that is, an exposure record that is invisible to the unaided eye.

When the photosensitive material is exposed, it is then developed to form a visible image. Development is carried out by applying a photosensitive material to a reducing agent (developer). This reducing agent is oxidized,
In the process of being oxidized, the exposure-dependent part of the silver halide is converted into metallic silver. This metallic silver is visible and in black and white photographs it forms a visible record.
In color photography, the oxidized reducing agent reacts with the dye precursor (coupler) to form a visible dye record.

Since the formation of a visible image is exposure dependent,
In the field of photography, the primary purpose is to increase the sensitivity of light-sensitive materials to light. Increasing photosensitivity results in an increase in visible image density for each given level of exposure. Then, the image can be recorded as a photograph even in a poor light environment. In addition, it allows the construction of films that produce excellent image quality.

The sensitivity (also called "speed") of silver halide grains, typically contained in gelatinous emulsions,
It is known to improve by including various non-silver or non-halide impurities in its internal structure. Such impurities are called doping agents and they are typically added during the precipitation of silver halide. Examples of doping agents are described in European patent applications 0325235 and 0.
475298, as well as U.S. Pat. No. 4,835,093.
And No. 4,933,272.

It is also known to incorporate impurities on the surface of silver halide grains in order to achieve sensitization.
Such impurities are called particle surface modifiers; these are
After precipitation or ripening they are added to photographic emulsions; these are described in US Pat. Nos. 5,256,530 and 5,252,451.
Issue. Other means of increasing the sensitivity of silver halide emulsions include adjusting the pH and / or pAg of the emulsion. In addition, photographic sensitivity can be increased by adding a certain type of chemical sensitizer, typically as a grain surface modifier. Several types of sensitizers are known. Most prevalent are gold and sulfur compounds, both of which are believed to enhance emulsion speed by forming electron or photohole traps on the silver halide crystal surface.

Sensitization has also been accomplished by the addition of other transition metals. Specifically, platinum salts are used, but gelatin sensitization significantly delays the sensitization by platinum salts. Furthermore, iridium salts and complex ions of rhodium, osmium and ruthenium have been used as chemical sensitizers. The overall effect on the sensitivity of these metals appears to depend on their valence state.

Reduction sensitization is another means by which sensitivity can be increased. Known reduction sensitizers include stannous chloride, ascorbic acid (European Patent Application No. 03694).
91 and 0369424) and dimethylamine borane (US Pat.
150,093 and 3,782,959).

The use of such sensitizers often leads to indiscriminate and undesirable reduction of silver ions to silver atoms. This silver atom causes a general or partial development density during development that is not associated with the effects of imaging exposure. This density is typically called fog,
And for negative elements, D-logE of the element
It is measured as the minimum concentration on the curve (Dmin); for positive (inversion) elements it is measured as the% of Dmin relative to Dmax in a standard 6-minute E6 rehalogenation process.

In sensitized silver halide photographic elements, fog formation is often controlled by the addition of oxidants which interfere with the reduction of silver ions to metal ions (or the opposite reaction). However, the addition of such an oxidant needs to balance the desensitizing effect of the oxidant and the sensitizing effect of the sensitizer, and it is difficult to achieve the balance.

[0011]

Accordingly, it is desirable to provide a light-sensitive photographic element that exhibits high sensitivity and that does not require the addition of an oxidant to control fog formation. Silver halide photographic elements, especially sensitized ones, are often desensitized when subjected to mechanical pressure. This problem is exacerbated in elements containing silver halide grains greater than 1 micron in size; in elements containing tabular crystal form silver halide grains, the problem is even greater.

Accordingly, it would also be desirable to provide a photosensitive photographic element which exhibits high sensitivity, but which, when subjected to mechanical pressure, exhibits high sensitivity without further substantial desensitization.

[0013]

The present invention provides a photographic element comprising a silver halide emulsion, said emulsion comprising silver halide grains containing an alkynylamine doping agent. To do. The presence of the alkynylamine doping agent imparts sensitive and advantageous properties to the photographic element. This property can be achieved without the need for the addition of oxidants to control fog formation. This property can also be realized without adversely affecting the sensitivity of the photographic element to pressure-induced desensitization. These and other advantages of the invention will be apparent from the description below.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Certain alkynyl amines, when included in photographic emulsions as grain surface modifiers,
Regarding the ability of increasing the speed and stabilizing the latent image, which is represented by the following structure, US Pat.
Nos. 378,426 and 4,451,557 are described:

[0015]

[Chemical 1]

In the above formula, X is

[0017]

[Chemical 2]

Y ¹ and Y ² individually represent hydrogen or an aromatic nucleus or an atom which together forms a fused aromatic nucleus; Z is

[0019]

[Chemical 3]

R is hydrogen or 1 to 5 carbon atoms.
Is lower alkyl; and R ¹ is hydrogen or methyl. In the present invention, when alkynylamines are used as a doping agent in a photographic element (a doping agent as used herein is a compound added to a photographic emulsion during precipitation of silver halide grains of the emulsion). It turned out, surprisingly, that the speed advantages mentioned above are also obtained. Further, the speed advantages described above can be achieved without substantially affecting the sensitivity of the photographic element to pressure-induced desensitization.

For the present invention, it has also been found that certain subclasses of compounds within the class of compounds represented by the above structures produce a significantly greater increase in sensitivity than the rest of the compounds within the class. This invention relates to a photographic element comprising silver halide grains containing a compound of the formula: Y-NHCH ₂ C≡CR ³ wherein R ³ is a hydrogen atom, an aliphatic group, a carbocyclic group. A group (including aryl) or a heterocyclic group, which may be substituted or unsubstituted. Preferably R ³ is other than hydrogen. More preferably,
It is an alkyl having 1 to 20 carbon atoms. Most preferably, it is a methyl group.

Examples of suitable aliphatic groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, isopropyl, t-butyl, butenyl, propynyl and butynyl. To be Examples of suitable carbocyclic groups are phenyl, tolyl, naphthyl, cyclohexyl, cycloheptatrienyl, cyclooctatrienyl, cyclononatrienyl, p-methoxyphenyl and p-chlorophenyl.

Examples of suitable heterocyclic groups are pyrrole, furan, tetrahydrofuran, pyridine, picoline, piperidine, morpholine, pyrrolidine, thiophene, oxazole, thiazole, imidazole, selenazole, tellurazole, triazole, tetrazole and oxadiazole. is there. The substituent represented by Y is preferably a nitrogen-containing heterocycle (including a heterocyclic ring system of two or more condensed rings). Therefore, Y
Include substituted and unsubstituted oxazoles, thiazoles, selenazoles, oxadiazoles, thiadiazoles, triazoles, tetrazoles, pyrimidines, pyrroles, pyridines, quinolines and benzimidazoles. . Preferably Y is a nitrogen containing azole.

Suitable groups for the substituents on Y (also R ³ ) include alkyl groups (eg methyl, ethyl,
Hexyl), fluoroalkyl groups (eg trifluoromethyl), alkoxy groups (eg methoxy, ethoxy, octyloxy groups), aryl groups (eg phenyl, naphthyl, tolyl), halogen groups, aryloxy groups (eg phenoxy). ), An alkylthio group (eg,
Methylthio, butylthio), arylthio groups (eg,
Phenylthio), acyl groups (eg acetyl, propionyl, butyryl, valeryl), sulfonyl groups, acylamino groups, sulfonylamino groups, cyano groups and acyloxy groups (eg acetoxy, benzooxy).

Preferred alkynylamines are those in which the alkynylamine is substituted on the carbon of the N = C component as shown in the structure below:

[0026]

[Chemical 4]

In the above formula, Z represents the atoms necessary to complete a 5 to 9 membered heterocyclic ring system, preferably a 9 membered fused heteroaromatic ring system such as benzoxazole. R ³ of this structure is defined as above. The most preferred alkynylamines contain a benzoxazole, benzoselenazole, or benzothiazole moiety and are represented by the structure:

[0028]

[Chemical 5]

Wherein X represents a substituted or unsubstituted nitrogen; or oxygen, sulfur or selenium, preferably oxygen; R ³ is as defined above; and R ²
And R ⁴ independently represent hydrogen, halogen, or a substituted or unsubstituted alkyl or alkoxy group, preferably having 1 to 10 carbon atoms. In the above alkynylamines, R ² and R ⁴ are preferably in the 6 and 5 positions, respectively. In such cases, the compounds of the invention may have the following substituents for X, R ² , R ³ and R ⁴ . This list is exemplary and not limiting of the invention, as other substituents are intended to be within the scope of the invention.

[0030]

[Table 1]

Specific compounds contemplated to be within the scope of this invention include the following:

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

The silver halide grains of the photographic emulsion of the present invention are
Precipitation is preferably in the presence of about 0.001 to about 5.0 millimoles of alkynylamine doping agent per mole of silver. A more preferred inclusion level of alkynylamine is
It is from about 0.002 to about 1 millimoles per mole of silver; more preferred levels are from about 0.005 to about 0.1 millimoles per mole of silver.

The preferred level of alkynylamine may also vary depending on the particular doping agent, the particular step during precipitation of adding the doping agent, and the particular effect desired. For example, compound G is the outer 3
For elements present at 8% precipitation, it is desirable to use levels of less than 1.0 mmol / mol silver. Ideally, a level of less than 0.1 mmol / mol silver is used.

For similar elements where the doping agent is present when the outer 10% of each grain is precipitated, less than 0.003 millimoles per mole of silver; most preferably 0.002.
It is preferred to use less than millimolar. The alkynylamines of this invention may be added to the black-and-white emulsion or color emulsion at any time during the formation of the silver halide grains, ideally during the precipitation of the silver halide. Specifically, the alkynylamine is preferably added after about 60% of silver halide is precipitated. More preferably, the alkynylamine is added to the emulsion after about 90% of the silver halide has been precipitated. In the above case, the alkynylamines are bound to each particle, for example, 20 to 70.
%) Is intended to be within the scope of the invention, but it is intended to add the alkynylamine by the time 98% of the silver halide is precipitated. Generally, it is not necessary, but desirable, that the alkynylamine be included during formation of at least 10% of the volume of the silver halide grain.

The above compounds are preferably added to an emulsion mainly composed of silver iodobromide. The advantages of the present invention are the halogenation of any type (silver bromide, silver chloride or silver iodide, or mixtures thereof) or any shape (ie cubic, octahedral, dodecahedral, spherical or tabular). A silver iodide content of less than 30 mol% is preferred, although it is specifically intended to be present in the case of emulsions containing silver grains. 1
More preferred are emulsions containing less than 0% silver iodide, the balance of the halide being silver bromide and / or silver chloride.

As mentioned above, the present invention may be practiced with silver halide grains of any shape (ie cubic, octahedral, dodecahedral, spherical or tabular). However, the invention is preferably practiced with tabular grains having an aspect ratio of greater than 2: 1, preferably at least 5: 1, and optimally at least 7: 1. “Aspect ratio” as used herein means the ratio of the equivalent circular diameter of a particle to the thickness of the particle. The equivalent circular diameter of a particle is the diameter of a circle having an area equal to the projected area of the particle.

The photographic elements of this invention can be single color elements or multicolor elements. Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the visible spectrum. Each unit can consist of a single emulsion layer or multiple emulsion layers sensitive to the spectrum of a given area. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the photographic art.

A typical multicolor photographic element is a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer combined with at least one cyan dye-forming coupler, at least one magenta dye. A magenta image-forming unit comprising at least one green-sensitive silver halide emulsion layer in combination with a forming coupler and at least one blue-sensitive silver halide emulsion layer in combination with at least one yellow dye-forming coupler. It comprises a support bearing a yellow dye-forming unit comprising. The elements of the invention may include additional layers such as filter layers, interlayers, overcoat layers and subbing layers.

According to a particularly preferred embodiment of the invention, the alkynylamine doping agents according to the invention are used in the yellow dye-forming blue-sensitive layer, preferably in the yellow dye-forming blue-sensitive layer of reversal films. The photographic elements of the present invention are also described in U.S. Pat. Nos. 4,279,945 and 4,302,523.
As described above, a transparent magnetic recording layer such as a layer containing magnetic particles may be contained under the transparent support. Typically,
The total thickness of the element (excluding the support) is about 5 to about 30 microns.

The following discussion of suitable materials for use in the elements of the present invention is set forth in Research Disclosur.
e , December 1978, Item 17643 and R.
esearch Disclosure , 1989 1
February, Item 308119, (both Kenneth Ma
son Publications, Ltd., Dudley Annex, 12a, NorthSt
reet, Emsworth, Hampshire PO10, 7DQ, England). This publication is referred to below as "Research
abbreviated as “Ch Disclosure”. The above Re
References to specific sections of the Search Disclosure are referred to above in the Research Disclosure.
Corresponds to each appropriate section of ure . The elements of the invention are
It comprises the emulsions and addenda described in these publications and the publications cited in these publications.

As stated above, the silver halide emulsions used in the elements of this invention include silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, salts. It can be silver bromoiodide or a mixture thereof. These emulsions are
The silver halide grains of any conventional shape or size can be included. Specifically, these emulsions can contain coarse silver halide grains, medium silver halide grains or fine silver halide grains. High aspect ratio tabular grain emulsions are specifically contemplated and include, for example:
Wilgus et al., U.S. Pat. No. 4,434,226, D
Aubendiek et al., No. 4,414,310, We.
y 4,399,215, Solberg et al. 4,433,048, Mignot 4,386.
156, Evans et al., 4,504,570, M.
Askasky No. 4,400,463, Wey et al. No. 4,414,306, Maskasky No. 4,4.
35,501 and 4,643,966 and Daubendiek et al., 4,672,027 and 4,693,964, all of which are incorporated herein by reference. Include). Also specifically contemplated are silver bromoiodide grains that have a higher molar ratio of iodine in the core of the grain than in the periphery of the grain, such as
British Patent No. 1,027,146, JP-A-54-485
21, U.S. Pat. Nos. 4,379,837 and 4,44.
4,877, 4,665,012, 4,68
No. 6,178, No. 4,565,778, No. 4,72
No. 8,602, No. 4,668,614, No. 4,63
6,461 and EP 264,954 or the specification. All of these are incorporated herein by reference. These silver halide emulsions can be precipitated as either monodisperse or polydisperse. The grain size distribution of the emulsion can be adjusted by a silver halide grain separation method or by blending silver halide emulsions of various grain sizes.

Additional doping agents such as copper, thallium, lead, bismuth, cadmium and Group VIII noble metal compounds can be present during the precipitation of the silver halide emulsion. Other doping agents include US Pat.
81,781, 4,937,180 and 4,
The transition metal complex salt described in 933,272 is mentioned.

The emulsion is a surface-sensitive emulsion, that is, an emulsion that forms a latent image mainly on the surface of silver halide grains, or an internal latent image-forming emulsion, that is, a latent image that is mainly formed inside a silver halide grain. It can be an image-forming emulsion. These emulsions are either negative-working emulsions, such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions, or unfogged internal latent image-forming direct positive emulsions. Thus, they behave positively when exposed to uniform light or developed in the presence of nucleating agents.

These silver halide emulsions can be further surface sensitized. Noble metals (eg gold), intermediate chalcogens (eg sulfur, selenium or tellurium) and reduction sensitizers used individually or in combination are specifically contemplated. Typical chemical sensitizers are the Research mentioned above.
Disclosure , Item 308119, No.
Listed in Section III.

These silver halide emulsions can be spectrally sensitized with dyes derived from various classes including polymethine dyes. These dyes include cyanine,
Mention is made of merocyanines, complex cyanines and merocyanines (ie trinuclear, tetranuclear and polynuclear cyanines and merocyanines), oxonol, hemioxonol, styrylyl, merostyrrylyl and streptocyanines. A specific spectral sensitizing dye is the above-mentioned Resea.
rch Disclosure , Item 30811
9, section IV.

Suitable vehicles for the emulsion layers and other layers of the elements of this invention are Research Discls.
Osure , Item 308119, Section IX and publications cited therein. The elements of the present invention are described in Research Disclosure , No. V
Couplers as described in Section II, paragraphs D, E, F and G and the references cited therein may be included. These couplers are based on Research Di
It can be included as described in sclosure , Section VII, paragraph C and the references cited therein. Research Disclosure
e , Item 308119, Section VII, paragraph F
Elements further comprising the image-modifying couplers described in 1. are also contemplated.

The photographic element of the present invention comprises an optical brightener ( Res
earl Disclosure , Section V), antifoggants and stabilizers such as mercaptoazoles (eg 1- (3-ureidophenyl) -5-mercaptotetrazole), azolium salts (eg 3-methylbenzothiazolium tetra). Fluoroborate), thiosulfonate salts (eg p-toluenethiosulfonate potassium salt), tetraazaindenes (eg 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and Research Disclosure ,
Section VI, Antifouling Agents and Image Dye Stabilizers ( Resea
rch Disclosure , Section VII, paragraphs I and J), light absorbers and scattering materials ( Rearse
ch Disclosure , Section VIII), Hardener ( R
research Disclosure , Section X), coating aid ( Research Disclosure , Section X)
Section XI), plasticizers and lubricants ( Research Dis)
Closure , Section XII), Antistatic agent ( Resea
rch Disclosure, Section XIII), matting agents (Research Disclosure, Section XII and Section XVI) and development modifiers (Researc
h Disclosure , Section XXI).

These photographic elements are Research D
It can be coated on a variety of supports as described in isclosure , Section XVII and references cited therein. These photographic elements are typically exposed to actinic radiation in the visible region of the spectrum, Research
A latent image as described in Disclosure , Section XVIII is formed and then processed to Research.
A visible dye image can be formed as described in Disclosure , Section XIX. The step of forming a visible dye image involves contacting the element with a color developing agent,
The step of reducing developable silver halide and oxidizing the color developing agent is included. The oxidized color developing agent in turn reacts with the coupler to yield a dye.

Preferred color developing agents include p-phenylenediamines. Particularly preferred is
4-Amino-3-methyl-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N- (β
-Methanesulfonamidoethyl) aniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N- (β-
Hydroxyethyl) aniline sulfate, 4-amino-3-
(Β-Methanesulfonamidoethyl) -N, N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-
(Β-methoxyethyl) -m-toluidine di-p-toluenesulfonic acid may be mentioned.

With negative-working silver halide emulsions this processing step provides a negative image. The elements are, for example, British Journal of Photograph Annual , 1988,196.
It can be processed by the known C-41 coloring process as described on page 198. Positive (or inverted)
In order to obtain an image, this color development step first develops the exposed silver halide with a non-color developing agent (no dye is formed) and then uniformly fogs the element to produce an unexposed halogenation. The silver can be developable. The reversal process of the element of the present invention is preferably Research
Performed by the known E6 treatment described and cited in Disclosure , paragraph XIX. Alternatively, direct positive emulsions can be used to obtain a positive image.

Development is followed by conventional bleaching, fixing or bleach-fixing steps to remove silver and silver halide, washing and drying. The present invention is also expected to produce photographic elements which have excellent raw material storage and, at the same time, excellent latent image stability. The present invention also provides a photographically effective amount of
Structure: Y-NHCH ₂ C≡CR ^{3 In the} above formula, R ³ is a hydrogen atom, an aliphatic, a carbocyclic or a heterocyclic group, which may be substituted or unsubstituted. And Y represents a nitrogen-containing heterocyclic component,
And a method comprising precipitating silver halide grains of a silver halide emulsion in the presence of a doping agent having

Photographically effective amount means the amount required to achieve a certain photographic effect; that is, the amount required to increase sensitivity. An example of an amount of alkynylamine effective to enhance sensitivity is from about 0.001 mmole to about 5.0 mmole per mole of silver.
Is. Preferred embodiments of the method according to the invention (eg preferred doping agents and their level of use) are apparent from the foregoing disclosure. It is also understood that the precipitation conditions of the present invention can be varied according to those commonly known in the art. For example, in a preferred embodiment, parameters such as pAg and pH can range from about 7 to about 10 and about 2 to about 7, respectively. The temperature during precipitation can range from 40 to 80 ° C, although temperatures outside this range are also specifically contemplated.

The present invention will be described more specifically with reference to the following representative examples.

Examples The compounds of this invention may be made by any method known in the art. Examples of such manufacturing methods are described in US Pat. Nos. 4,451,557 and 4,3.
78,426, both of which are incorporated herein by reference.

The following examples are tabular emulsions of silver bromide and silver iodobromide with average diameters greater than or equal to 0.3 micron, aspect ratios greater than 7: 1, and of the projected area of the micrograph. An emulsion was used in which at least 50% were grains as described above. Net iodide content is 0% to 3
It was in the range of%. Iodide, if present, was introduced by uniform addition, discontinuous introduction of iodide-rich seed emulsion or soluble iodide salt, or any combination of these methods. In all examples, an organic solution of alkynylamine was introduced into the precipitation reactor during the latter half of particle growth. The emulsion thus treated was then chemically and spectrally sensitized.

Example 1: Tabular Ag with a uniform iodide phase
BrI emulsion A silver iodobromide tabular grain emulsion was precipitated and washed according to conventional methods. The reactor was charged with a solution containing water, a peptizer and a halogenated salt such as NaBr. Double-jet addition of a soluble silver salt and halide salt mixture with vigorous mixing results in nucleation of AgBrI tabular grains at a temperature of 30 to 50 ° C. and a pH of 3.5 or less.
The pAg was 9.
It became 0-10.5. Iodide was present at levels up to 3 mol%. The ripening agent was present at levels up to 0.5 mole per mole of silver nucleated. Following nucleation, additional peptizer is added and the reactor conditions are set to a temperature of 40-80.
C; pH 5.0-6.0; and pAg 8.6-9.0
I adjusted it to be.

Specifically, control emulsions A and C (AgB
r _.97 I _.03) was prepared according to the scheme, to produce a tabular emulsion having an average thickness of 0.15 microns and an equivalent circular diameter 2.7 microns. Example emulsions of this invention were similarly prepared up to a certain percentage of total precipitated silver (G). At this point (G), a solution of alkynylamine in a suitable solvent was added to the reaction mixture, which was then briefly quiescent. A
Double jet precipitation of gBr was then resumed for the remaining 100-Q percent of total silver halide. The physical size of the chemically treated emulsion and the crystal form of the grains were indistinguishable from the control emulsion.

Each emulsion was run at the optimum speed /
It was subjected to a sensitizing process that was specified to give fog performance. The main components per mol of silver halide were as follows: benzoxazoocyanine sensitizing dye 1.2 × 10.
^-3 mole; Gold from unstable gold reagent 6.6 × 10 ^-6 mole;
And sulfur from unstable sulfiding agents 3.1 × 10 ^-5 mol
e.

Other adjuvants such as thiocyanate and benzothiazolium salts were also added. The chemical ripening was carried out by applying a heat cycle that was set so as to minimize fog at an optimum speed. In these experiments,
A 10 minute hold at 63 ° C was used. Stabilizer, 5-methyl-
The sodium salt of 5-triazol-2,3-pyrimidin-7-ol was then added.

Antihalation combinations of suitable dye-forming couplers and a mixture of additional gelatin colloidal dispersions and sensitized emulsions with a surfactant necessary for uniform development with a hardener on a transparent support. It was applied together with a protective agent. The dry coating was step-exposed using a Type I-b sensitometer, the sensitometer
ten (Eastman Kodak Company)
(Registered trademark) Type 2B filter for removing ultraviolet rays from a light source having a color temperature of 5500K. This coating is then processed according to standard process E-6 known in the art to obtain a color reversal dye image, or C-4 which is also known in the art.
1 to obtain a negative dye image. Relative reversal speed was measured as the difference in exposure required to reduce the maximum dye density by a fixed amount, specifically 0.3. Relative negative speed was measured at a point 0.15 above Dmin.

In the table below, Emulsions A and B are referred to as Emulsion C.
~ G represent different coatings. Relative speed is expressed in 100 ^* log (exposure) units relative to the control. Fog is
As a percentage of Dmin to Dmax in the standard 6-minute E6-rehalogenation process, or 3.25 minutes C-4.
Expressed as Dmin in Method 1. The results are summarized in Table II. The quantities are expressed in moles of compound G per final mole of precipitated silver halide. Treatment with alkynylaminobenzoxazole during precipitation resulted in a substantial speed increase. Speed increases were observed with both E-6 and C-41 (both treatments of commercial importance). Fog increase was minimal when a small amount of alkynylamine was included (see Emulsions B, D, E and G). Emulsion G shows that a speed increase of more than one stop is obtained while the fog increase remains small.

[0065]

[Table 2]

Sensitivity to pressure-induced desensitization was measured by comparing sensitometric curves with and without mechanical pressure applied to the film using a mechanical pinch roller. The difference in exposure dose required to obtain a constant density (D = 0.5) in the leg region of the inversion curve is a quantitative measure of desensitization expressed as delta-leg (DEL-TOE). Ideally, a value of 0.0 is desirable as this guideline. Comparative Emulsion X was a 3% iodide tabular emulsion of essentially the same size as above, where the iodide temporarily dumped the AgI seed emulsion.
It was introduced as an antennaous dump). The results are shown in Table III.

[0067]

[Table 3]

Control Emulsion X shows good speed but
When mechanical pressure was applied, it showed high speed with the sacrifice of desensitization. Control emulsions A and C showed low desensitization but poor speed even when mechanical pressure was applied. Emulsions B and D
Had sufficient speed and had little or no sensitivity to pressure-induced desensitization.

Example 2 Non-uniform iodide phase structure tabular emulsion emulsions I to N were silver iodobromide tabular grain emulsions having a bulk iodide content of 2%. Iodide was introduced as an AgI seed emulsion dump after 55% of the total silver halide had precipitated. It has been found that the iodide is incorporated into the AgBr main population by recrystallization, introducing an iodide phase having an iodide content substantially greater than the bulk or average iodide content of the grains.

The precipitation was carried out in a reactor charged with water, a peptizer and a halide salt such as sodium bromide. Nucleation was carried out with vigorous stirring at 40 ° C, pAg 1
It was carried out by adding a single jet of soluble silver salt at pH 0 and pH 5.8. The temperature was then raised to 60 ° C. and then the peptizer and water were added along with the halide or salt and the acid or base necessary to obtain the proper conditions for crystal growth (eg pH). Twinning grew upon double jet addition of soluble silver and bromide salts at pAg 9.3, pH 6.0 and always in halide excess. After precipitation of 50% silver,
The halide excess was reduced to a pAg of 7.9. In this low halide excess state, double jet precipitation was performed using silver 55
% Until precipitation, at which time a certain amount of iodide-rich seed emulsion (Lippmann AgI) was introduced. Precipitation was continued in the presence of low halide excess until 62% silver was precipitated. At this point, one of the alkynylamines of the invention (non-control emulsion) was added and then allowed to stand for an appropriate length of time. The rest of the precipitation was done with a similar low halide excess. The emulsion was then concentrated to remove excess electrolyte.

The emulsions of the invention had equal average grain sizes of 1 micron and average thickness of 0.1 micron. Emulsions J-N were prepared the same as Control I, except that the alkynylamine doping agent was added to the reactor at that point.
All emulsions were sensitized, as described in Example 1 above, under conditions designed to give each emulsion low fog and optimum speed. The coating and test procedure was as described above.

The results obtained from standard reversal and negative treatments of model coatings are summarized in Table IV.

[0073]

[Table 4]

As can be seen from Table IV, inclusion of varying levels of alkynylamine doping agents during the precipitation of a substantial portion of each silver halide grain of a photographic element results in an element with a significant increase in speed. Such particles can be obtained substantially without fog formation. Although the invention has been described in detail with reference to its preferred embodiments, it will be understood that the invention can be altered and modified within the spirit and scope.

[0075]

[Additional Embodiment]

<Aspect 1> The alkynylamine doping agent is
Structure: Y-NHCH ₂ C≡CR ^{3 In the} above formula, R ³ is a hydrogen atom, an aliphatic, a carbocyclic or a heterocyclic group, which may be substituted or unsubstituted. The photographic element; and Y represents a nitrogen-containing heterocyclic element. <Aspect 2> The alkynylamine doping agent is
Construction:

[0076]

[Chemical 9]

Wherein Z represents an atom necessary to complete a 5-9 membered heterocyclic ring system; and R ³ is as defined above. Photo element. <Aspect 3> The alkynylamine doping agent is
Construction:

[0078]

[Chemical 10]

In the above formula, X represents a substituted or unsubstituted nitrogen; or oxygen, sulfur or selenium;
A photographic element according to embodiment 1 having R ³ as defined above; R ² and R ⁴ independently represent hydrogen, halogen or a substituted or unsubstituted alkyl or alkoxy group. <Aspect 4> The photographic element according to aspect 1, wherein R ³ is other than hydrogen. <Aspect 5> A photographic element according to Aspect 4, wherein R ³ is methyl. <Aspect 6> A photographic element according to Aspect 3, wherein X is oxygen. <Aspect 7> The photographic element according to aspect 6, wherein the silver halide grains are composed of silver bromide or silver iodobromide. <Aspect 8> The photographic element according to Aspect 7, wherein the silver halide grains are made of silver iodobromide. Aspect 9 The photographic element of aspect 6 wherein the silver halide emulsion comprises tabular silver halide grains having an aspect ratio of greater than about 7: 1. <Aspect 10> The photographic element according to Aspect 9, wherein the alkynylamine doping agent is contained in the silver halide emulsion in an amount of about 0.001 mmole per mol of silver to about 5.0 mmole per mol of silver. <Aspect 11> The photographic element according to Aspect 10, wherein the alkynylamine doping agent is contained in the silver halide emulsion in an amount of about 0.002 mmole per mol of silver to about 1.0 mmole per mol of silver. <Aspect 12> The photographic element according to aspect 11, wherein the alkynylamine doping agent is contained in the silver halide emulsion in an amount of about 0.005 mmole per silver mole to about 0.1 mmole per silver mole. <Aspect 13> The alkynylamine doping agent is

[0080]

[Chemical 11]

[0081]

[Chemical 12]

A photographic element according to aspect 12 selected from the group consisting of: <Aspect 14> A photographically effective amount of the structure: Y-NHCH ₂ C≡CR ^{3 In the} above formula, R ³ is a hydrogen atom, an aliphatic, a carbocyclic or an alicyclic group, and may be substituted. And Y is a nitrogen-containing heterocyclic component, the method comprising the steps of: precipitating silver halide grains of a silver halide emulsion in the presence of a doping agent. <Aspect 15> The method according to Aspect 16, wherein the silver halide grains are precipitated in the presence of a doping agent in an amount equal to about 0.001 mmole per silver mole to about 5 mmole per silver mole. Aspect 16 A photographic element comprising silver halide grains doped with a photographically effective amount of a nitrogen containing heterocyclic akinylamine.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Roger Lock, New York, USA 14610, Rochester, Dorchester Road 204

Claims (1)

[Claims] 1. A photographic element comprising a silver halide emulsion, said emulsion comprising silver halide grains containing an alkynylamine doping agent.